DRAFTING A SUITABLE METHOD FOR BLACKENING OUTER SURFACE OF COPPER ABSORBER FOR USE IN SOLAR TECHNOLOGY Jn Pagik1), Radim

Rybr2),
Abstract In this contribution we are dealing with appropriate methods to create a black coating on the copper absorber and we define three ways to create blackened copper. We want to preserve the simplicity, efficiency and low cost of each investigational methods. Black thin film of cobalt and black chrome formed on copper foam absorbers can be produced by galvanic method. The goal is to examine the influence of the metalic substrate, process of heat treatment on the surface of the material, and also changes in the morphology, absorption and reflectance. The surface morphology in close-up view revealed and clearly showed us that the black film of cobalt and chromium has a porous structure. Therefore the absorption capacity of such films is more than !", which is appropriate for use as a solar absorber. Key words: Thermal emissivity, and bsorbcia solar absorber black chrome, black cobalt, copper oxide, electrochemical deposition, electrolysis, solar technology, selective surface,

INTRODUCTION TO COPPER COATING METHODS

#ost optically active selective coatings for solar absorbers combine high amount of absorption of solar radiation with low thermal emissivity. $ffective selective absorption of these layers is brought about by the presence of the surface layer, which absorbs the entire solar spectrum, and almost does not permit the infrared radiation to escape. In other words, these selective coatings have high absorption capacity and low solar heat reflectance of the reflecting metal substrate, due to surface deposition of suitable black material. %enerally for the substrate we can use metals such as copper, nickel, aluminum or steel. It is well known that the optical properties are highly determined with the metal content and also the microstructure of thin absorbent film. &bsorption film should absorb the entire spectrum of sunlight without losing heat energy from surface reflection. Ideal selective coating could fully absorb the wavelengths of less than '(m and completely reflect wavelengths greater than '(m. By the Influence of temperature, p) and composition of the reactants and thus the current density, we can control the formation progress of thin film in electrochemical deposition.

SELECTIVE ABSORPTION COATINGS

There are several selective coatings known, suitable for use in solar technology as absorbers. They are produced by electroplating and chemical transformation of the surface layer of the metal absorber. *ayer of black chromium is prepared by plating the chromium oxide on the nickel-plated copper. Black copper +copper oxide, is prepared by using sodium hydroxide, potassium persulfate, or by *-. +liver of sulfur,. Black cobalt is formed by electrolysis of copper sulfate on the copper nickel-plated substrate. The spectral reflectance of the visible and infrared spectrum is measured using a spectrophotometer +/erkin-$lmer,. Th bas!c "ara# t rs $%r & t r#!'!'( th s)!tab!*!t+ %$ s * ct!, s)r$ac s-

T t 2 3

Temperature ........................................... 01 Time ........................................................... s .olar &bsorptance Thermal $mittance

1.1 C%ba*t s * ct!, s)r$ac This method belongs to the class of coatings, which is very effective for use in solar technology as a absorber coating method. It4s formed by chemical process called conversion. /reparative aspects of thin cobalt oxide films were examined by different sub5ects, because of their numerous applications in various fields of technology. We will only exam the application for solar thermal energy as a selective absorbent layer for collectors. .pectrally selective surfaces exhibit high values of 2, ie the absorption of solar radiation and low values of thermal radiation +3, 678. They also improve the thermal efficiency of the solar collectors by reducing heat loss caused by radiation 6'8. These surfaces are used as receiving coatings 9 likr surfaces of thin plate collectors or vacuum tube collectors. :nder ideal conditions they can withstand temperatures of ;!! 01. #any types of coatings have been developed, which have potential for use as selective absorbers 6<8. &ttractive target for the study of selective surfaces is the development of one type of coating 9 paint, that could be used for all designs of solar collectors. =or successful industrial development of such coating, the coating must not only have favorable optical properties, but also to be easily reproducible, durable, thermally stable and inexpensive to produce. &lthough the cobalt oxides or let4s say selective cobalt coating are also proposed for solar systems, to work in the operating temperatures of <!!-;!! 01, little is known about their stability and degradation during prolonged exposure to high temperatures 6>8. ?ue to the fact that it is a method of chemical conversion processes, it is appropriate to describe the process of electrochemical preparation of cobalt oxide. It can be divided into two groups@ direct indirect

In the first case, the solution is prepared by dissolving the chemical components allowing for the direct preparation of black cobalt on the substrate on the cathode side in the electrolysis process 6;8. The indirect method is the formation of cobalt oxide carried out in two steps@ at first, layer of metal cobalt is formed on the nickel-plated copper base. then cobalt chemically or thermally oxidiAed to form a black cobalt 6B8.

?ue to its optical, semiconductor, magnetic and electrochemical properties, the black cobalt is the promising material among transition metal oxides, which makes it attractive for solar photochemical applications and absorbers for solar collectors 6C8. 1urrently, there are six physical absorption mechanisms of solar radiation 6D8. )owever, it is known, that one of the most effective mechanisms are the optical properties in the microstructure. Important parameters are also the textured surfaces, dependant on the morphology of the surface. These materials have a high absorption of solar radiation thanks to multiple reflection of the incident radiation between dendrites, which are about two microns apart, while longwave thermal radiation is not affected by such structure.

.everal methods are currently used to achieve these spectrally selective properties of black metal surfaces of solar absorbers. They are the methods of chemical conversion, thermal oxidation of thin metallic films and electrodeposition 6 8. .o to create a thin layer of black cobalt we have to use electrodeposition method on nickel plated copper substrate. The basis of this process is galvanic cell. The current goes through a bath containing the electrolyte, anode and cathode. &node is actually a metal, which will be coated on the cathode. The electrolyte is an electric conductor in which the current is carried by ions instead of free electrons, like in the conductor in electronics. When ?1 electric current passes through the electrolyte, the chemical reaction begins +oxidation 9 reduction,. Eeduction occurs at the cathode and oxidation occurs at the anode. $lectrolyte closes the circuit between the two electrodes. /ositive ions in the electrolyte are moving to the cathode, and negatively charged ions towards the anode. 1opper absorber should be thoroughly degreased and cleaned before electrolysis, then immersed for B! seconds in ;" sulfuric acid to improve nickel-plating process. 1onditions for successful nickel-plating and creation of a thin layer of black cobalt are presented in the following two tables +Table 7, Table '., 6;8.
Table 7. 1onditions for electrolytic deposition and bath composition for nickel-plating of copper absorber

Bath composition 6gl-78 Fickel sulfate ';! Fickel chloride ;! Boric acid ;!

?ensity of current flow 6&.dm-'8 !.;

Temperature 6018 C!

Table '. 1onditions for electrolytic deposition and bath composition for creating selective cobalt coating

Bath composition according to the 6gl-78 1obalt sulfate >!! 1obalt ;! Boric acid >! 1obalt nitrate >

?ensity of current flow 6&.dm-'8 <

Temperature 6018

p)

<!

>

The main source of cobalt ions is cobalt sulfate, cobalt chloride is good for conductivity of the electrolytic solution, boric acid is an eGuilibrium agent and cobalt nitrate produces the desired black layer. :pon completion of the electrolysis, the sample was annealed at >!! 0 1 for '! minutes to test the reGuired parameters of the sample. The resulting analysis of black cobalt absorbent coating is shown in =igure 7.

=igure 7. The relationship between wavelength and absorption of cobalt thin film on black copper absorber +black, before heat treatment +red, after heat treatment 678

1.2 B*ac/ chr%# a'& b*ac/ c%"" r %0!& c%at!'( We already know, that black chrome layer is obtained by plating chromium oxide on the nickel-plated copper. Hudging by the parameters it is similar method to the cobalt coating method. #any collector manufacturers indicate !- B" absorption values by using black chrome and emissions of about 7!-'!" as seen in =igure '.

=igure '. Eeflectance and absorption as a function of wavelength for samples with a black chrome coating 6 8

The maximum measured value of absorption for black chrome was !. ; with a minimum emissivity !.'! 6 8. These relatively good properties were obtained in a controlled electrolysis process. The coating thickness can be changed by alternating two parameters@ The duration of electrolysis ?ensity of current flow

The maximum measured value for the absorption of black copper oxide was !. D with a minimum emissivity !.7! 6 8. These excellent properties are achieved by a controlled course of a chemical reaction, which is dependent on@ The duration of the chemical reaction The samples were sub5ected to thermal load, to test their thermal stability, resistant to moisture and mechanical deformation. Tests did not show significant changes, which is good, considering later use of these methods in solar technology 6 8. &s an example, the following table +Table <, provides the comparison of emissivity values of different materials. Table <. The emissivity values of different materials S)r$ac Mat r!a* E#!ss!,!t+ C% $$!c! 't 1 2 1 &luminum foil !.!> &sbest board !. B &sphalt !. < /olished brass !.!< =ireclay brick !.C; 1oncrete !.D; /olished copper !.!'< to !.!;' .mooth glass =rom !. ' to !. > *ead - oxidiAed !.>< .teel =rom !.'! to !.<' /aper !. < /lastics !. 7 .and !.CB Water !. B Wood, pine !. ; Iinc polished !.!>; 1opper - electroplated !.!<

FINAL VALIDATION OF THE OBTAINED COATINGS

We comes to theory, that emissivity and absorption raises with increasing duration of deposition time and thus increases the thickness of the coating. The optimum thickness should not only have a high absorbance of solar radiation and low thermal emissivity, but also good

adhesion, good integrity, high-temperature stability and reproducibility. &nother important aspect in selective coatings from a commercial point of view is the current density. It is preferable that the current density is less than !.; &.cm -'. 1urrent density is directly dependent on the amount of acid in elecrolytic bath. %ood adhesion was obtained using a current density of 7!! <!! m&.cm-'.

CONCLUSION

The aim of this contribution was to select an appropriate method to blackened copper absorber for use in solar technology. We compared two methods. In the first method +black chrome selective surface and black cobalt, is used electrolytic plating, where we deposit the coating of cobalt or chromium on the copper metal. In the second method, the black color is achieved by establishing a copper oxide, using the chemical reaction. Black cobalt and black chrome seems like a good candidate, because of its high temperature selective absorber layer. :nlike to annealing, needed in second method, galvaniAing method gives an economic advantage, when there is direct production of black cobalt on the surface of the absorber.

R $ r 'c s 7. '. <. >. ;. B. C. D. . /e5ova, B., Isahi, &., Fa5doski, #. and %roAdanov, I. Fabrication and characterization of nano-cobalt oxide thin films, #aterial Eesearch Bulletin <B, '!!7, pp. 7B7-7C!. .hashikala, &.E., .harma, &.J., and Bhandari, ?.E. Solar selective black nickelcobalt coatings on aluminum alloys, .olar energy materials K .olar cells 7, '!!C, pp. B' -B<;. )utchins, #.%., Wright, /.H. and %rebenik, /.?. Comparision of different of black cobalt selective solar absorber surfaces, .olar energy materials 7B, 7 DC, pp. 77<7<7. 1houdhury, 1. and .ehgal, ).J. High temperature degradation in cobalt oxide selective absorber, .olar energy <!, 7 D<, pp. ' 7-' '. Barrera, $., %onAaleA, I. and Liveros, T. ne! cobalt electrodeposit bath for solar absorber, .olar energy materials and solar cells ;7, 7 D, pp. B -D'. &bdel )amid, I., &bdel &al, &. and .chmuki, /. "anostructured black cobalt coating for solar absorbers, .urf. Interface &nal >!, '!!D, pp. 7> <-7> . Barrera, 1.$., .algado, *., #orales, :. and %onAaleA, I. Solar bsorptance of black cobalt and black cobalt-silver films and its relation !ith roughness coefficient , Eenewable $nergy '>, '!!7, pp. <;C-<B>. Barrera, $., /ardave, #./., Batina, F. and %onAaleA, I. Formation #echanisms and Characterization of black and !hite cobalt $lectrodeposition onto Stainless Steel, Hournal of $lectrochemical .ociety 7>C, '!!!, pp. 7CDC-7C B. Luletin, H., JuliMiN, /., Bosanac, #. Selectively absorbing coatings, =aculty of $l. $ngineering, Hournal de physiGue, .plit, 7 D7

C%'tacts Ing. HOn /agONik

Technical university in Josice, =aculty of #ining $cology /rocess control and %eotechnology, Institute of Business and #anagement /ark JomenskPho, 7 , !>' !! JoMice Tel@ Q>'7 ;; B!' '><B email@ 5an.pagacikRtuke.sk doc. Ing. Eadim EybOr, /h?. Technical university in Josice, =aculty of #ining $cology /rocess control and %eotechnology, Institute of Business and #anagement /ark JomenskPho, 7 , !>' !! JoMice Tel@ Q>'7 ;; B!' '<D; email@ radim.rybarRtuke.sk